Sensitizing silver halide emulsions



April 25, 1939- w. DIETERLE 2,155,475

SENSITIZING SILVER HALIDE EMULSIONS Filed Oct. 20, 1936 Fig. I

llnsensitized Jfluer (fihrziie [mulsian Fig. 3

Inventor y His Attorney ht'alfer Dialer/e Patented Apr- 25, 1939 G SILVER HAIIDE IIIULBIONS Walter Dieter-lo, Deena, Germany, drums to m Amco Ca'poration, Binghamton, N. 1., a corporation of New York Application October 20, 1936, Serial No. 1.8.575

- V In Germany July 33, 1938 4 Claims. (01- 05-7) hereafter.

I have found that silver halide emulsions, especially silver chloride emulsions. can advantageously be sensitized with a polymethine dyestuil' which has been made by condensation of adiamineoratriaminewithanaidelrvde ofa heterocyclic nitrogen compound containing in a-position to the nitrogen atom a reactive methylene group and in which the aldehyde group stands in place of a hydrogen atom of the 50 methylene group.

These dyestuifs may be derived from dyestuils of the above mentioned class by using instead of the simple amine a diamine (triamlne) for the condensation and causing two (three) molecular proportions of aldehyde to react with one molecular proportion of dlamine (trlamine). The fundsmentalcharacter of these dyestutfs is essentially the same as that of the known class, only the color is somewhat poorer. Quite unexg pectedly it is found that these dyestuffs have'a sanitizing action.

naphthalene; X=haloeenorarmtheracidradicah Inthhformulaflieheterocyclicringsystems andalsothearomaticringsystem,whichcontaimtheamino-group,maycarryvazioussubstitucntamsemnsathosewhichmy have a pronounced injurious action on the sensitiaation.

Reference is made to the accompanying drawing in which there are represented spectograms of the same emulsion sensitized with my sensitizers.

-Fig. 1 shows for the sake of comparison the spectrogram of the unsensitlsed silver halide emulsion used for the tests.

Fig. 2 shows the spectrogram of the silver halide emulsion sensitised according to Example 1.

Fig. 3.shows the spectrogram of the silver halide emulsion sensitized according to Example 10.

Fig. 4 shows the spectrogram of the silver halide emulsion sensitized according to Example 13.

The art of producing photographic emulsions is thus enriched by a new class of sensitizers constituted by dyestuffs of an extensive group, the numbers of which present a great capacity for variation by the introduction of substituents.

The following examples serve to illustrate the invention: Emmm 1 20 parts by volume of per cent hydrochloric acid are diluted to parts with water, 10 parts of benzidine and 21 parts of 1,3,8-trimethyl-2- methylene-indoline-omega-aldehyde are added and the mixture heated for half an hour at about 100 C. The dyestufl which crystallizes out after cooling is filtered off by suction washed with a little water and dried under reduced pressure. The dye has the following formula:

C CHs The yield is about 29 parts. A silver chloride emulsion sensitised with the dyehas a maximum of sensitivity at a wave length of about 510 mu.

Emilie 2 By condensing 2 molecular proportions of 1,3,3- trimethyl -2-methylene-lndoline-omegaaldehyde with .1 molecular proportion of ortho-phenylenediamine the following dye is obtained OB: CHI OH; CH

A silver chloride emulsion sensitized with the dyehas a maximum of sensitivity at a wave lengthoiabouti'lilm trample 8 with 1 molecular proportion of 4,4' -diamino-3,3'- dichlorophenylmethane the following dye is ob- By condensing 2 molecular proportions of 133- tained:

CHI

trimethyl-2-methylene-indoline-omega-aldehyde A silver chloride emulsion sensitized with the with 1 molecular proportion of meta-phenylenedye has a of sensitivity at a wave diamine the following dye is obtained length of about 450 m.

cm on. on. o

a=onnn NHOH=-OK 0Q. Cl o( clh A silver chloride emulsion sensitized with the dye has a maximum of sensitivity at a wavelength of about 4'70 m Example 7 By condensing 2 molecular proportions of 1,3,3- trimethyl-Z-methyiene-indoline-omegaaldehyde with 1 molecular proportion of 5,5'-dia.mino-2,2'- methylene-diphenylsulfone the following dye is obtained Example 4 By condensing 2 molecular proportions 0! 1,8,8- trimethyl-2-methylene-indoline-omega -aldehyde dyehasamaximumofsensitivityatawave length of about 460 Inn.

with 1 molecular proportion of LIE-naphthalenediamine the following dye is obtained A silver chloride emulsion sensitized with the dye has a maximum 0! sensitivity at a wave length of about 480 m Example 8 By condensing 2 molecular proportions of 1,3,3-

Emmpze 5 trimethyl-2-methylene-indoline-omegaaldehyde with 1 molecular proportion of 4,4'-diamino-ben- By condensing 2 molecular proportions of 1,3,3- eophenone the ioliowing dye is obtained CHI CH;

CHI n O trimethyl-il-methylene-indoline-omega-aldehyde A silver chloride emulsion sensitized with the with 1 molecular proportion of 3,3'-4,4'-tolidine dye has a maximum of sensitivity at a wave the following dye is obtained length of about 480 m A silver chloride emulsion sensitized with the dye has a maximum of sensitivity at a wave length of about 490 m w;

Example 6 By condensing 2 molecular proportions of 1,3,8- trimethyi-2-methyiene-indoline-omesaaldehyde Example 9 ifipartsbyvolumeofhydrochloric aEidof a0 per cent strength are diluted with 100 parts by volume of water; to this mixture there are added 5,5 parts by weight of 4,4'-diaminostilbene and 12 parts by weight at lfifi-trimethylJ-methyisome A silver chloride emulsion sensitized with the dye has a maximum of sensitivity at a wave length of about 520 my. 7

25 By condensing 2 molecular proportions of 1,3,3-

.trimethyl-Z-methylene-indoline-omegaaldehyde with 1 molecular proportion of 4,4'-diaminodi phenylamine the following dye is obtained dyehasaol'auilflvityatawan lengtholaboutmm Emi e i3 nyeeneeiiemnmeieeuiu -e eruemeinbemimmie -methfleneomega aldehydewithlmolecularWrtionoiparv OHs phenylene-diamine the following dye is obtained:

A silver chloride emulsion it h has

dye has a maflmum of sensitivity at a wave v length of about 580 ms.

om cm on, a I 0 OH=OHNH-C NEONH;0H=OK dawn v cm A silver chloride emulsion with the dye has a maximum of sensitivity eta wave length 0! 580 m 5 By condensing 2 molecular-proportions oi 1.8.3- I trimethyl-S-methoxy-Z-methylene-indollne-omelie-aldehyde with 1 molecular proportion of 4,4 diamino-ma' dirnethoiwdiphenylmethane the following dye isobtained:

w A silver chloride emulsion sensitised with the dye has a maximum 01 sensitivity at a wave length 01. about 480 m Example 12 with 1 molecular proportion of para-phenylenediiimiriethe following dye is obtained:

momma-Okinawan CsKi (J1 O( fisfii 75' A silver chloride emulsion sensitised with the By condensing 2 molecular proportions oi lethyl-z-inethylene quinoline omega aldehyde What I claim is: 1. A silver halide emulsion comprising dye corresponding with the formula:

I @H-(lh-NH-Ar-NIh-OR-OEQ Soon;

in which food z stand lora member selectedirom wherein in than. me imalk yl mm. a

the group consisting oi. 8, Be, -CH-=C'H- and stands for alkyl, Ar stands for an aromatic radlcal which contains at least one benzene nucleus but no more than two bensene nuclei, x'stands iorananlenospablooiprecipitsting-themr in. we 5 (r m m on, Ol cm Gl 3. A silver halide emulsion containing the dye: 4. A silver halide emulsion containing the dye: I

WALTER DIETERLE.

' DISCLAIMER 2,155,475.Walter Dieterle, Dessau Germany. 'SmNsrnzma SILvEn HALIDE EMUL- axons. Patent dated April 25, 1939. Disclaimer filed March 14, 1941, by

the essignee, General Aniline & Film Corporation. .Hereb enters this disclaimer to claim 1 of the above patent. flcial Gazeite April 8, 1941.] r

in. we 5 (r m m on, Ol cm Gl 3. A silver halide emulsion containing the dye: 4. A silver halide emulsion containing the dye: I

WALTER DIETERLE.

' DISCLAIMER 2,155,475.Walter Dieterle, Dessau Germany. 'SmNsrnzma SILvEn HALIDE EMUL- axons. Patent dated April 25, 1939. Disclaimer filed March 14, 1941, by

the essignee, General Aniline & Film Corporation. .Hereb enters this disclaimer to claim 1 of the above patent. flcial Gazeite April 8, 1941.] r 

